WO2014204013A1 - Joining material and joining method using same - Google Patents

Joining material and joining method using same Download PDF

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Publication number
WO2014204013A1
WO2014204013A1 PCT/JP2014/066916 JP2014066916W WO2014204013A1 WO 2014204013 A1 WO2014204013 A1 WO 2014204013A1 JP 2014066916 W JP2014066916 W JP 2014066916W WO 2014204013 A1 WO2014204013 A1 WO 2014204013A1
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WO
WIPO (PCT)
Prior art keywords
silver
bonding material
mass
rpm
viscosity
Prior art date
Application number
PCT/JP2014/066916
Other languages
French (fr)
Japanese (ja)
Inventor
圭一 遠藤
実奈美 永岡
哲 栗田
宏昌 三好
佳子 河野
彰宏 宮澤
Original Assignee
Ｄｏｗａエレクトロニクス株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ｄｏｗａエレクトロニクス株式会社 filed Critical Ｄｏｗａエレクトロニクス株式会社
Priority to CN201480034825.3A priority Critical patent/CN105307801B/en
Priority to US14/899,858 priority patent/US10328534B2/en
Priority to EP14814197.1A priority patent/EP3012048B1/en
Priority to KR1020167001388A priority patent/KR102175686B1/en
Publication of WO2014204013A1 publication Critical patent/WO2014204013A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/3006—Ag as the principal constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/052—Metallic powder characterised by the size or surface area of the particles characterised by a mixture of particles of different sizes or by the particle size distribution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B22F1/0545—Dispersions or suspensions of nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/102—Metallic powder coated with organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/107—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing organic material comprising solvents, e.g. for slip casting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K1/00—Soldering, e.g. brazing, or unsoldering
    • B23K1/0008—Soldering, e.g. brazing, or unsoldering specially adapted for particular articles or work
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
    • B23K35/0244—Powders, particles or spheres; Preforms made therefrom
    • B23K35/025—Pastes, creams, slurries
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/25—Noble metals, i.e. Ag Au, Ir, Os, Pd, Pt, Rh, Ru
    • B22F2301/255—Silver or gold
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2303/00—Functional details of metal or compound in the powder or product
    • B22F2303/40—Layer in a composite stack of layers, workpiece or article
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2304/00—Physical aspects of the powder
    • B22F2304/05—Submicron size particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
    • B22F7/062—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools involving the connection or repairing of preformed parts
    • B22F7/064—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools involving the connection or repairing of preformed parts using an intermediate powder layer
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
    • H05K3/3457—Solder materials or compositions; Methods of application thereof
    • H05K3/3485—Applying solder paste, slurry or powder

Definitions

  • the present invention relates to a bonding material and a bonding method using the same, and more particularly to a bonding material made of a silver paste containing silver fine particles and a method for bonding objects to be bonded together using the bonding material.
  • the objects to be bonded can be bonded even in an inert atmosphere such as a nitrogen atmosphere.
  • fluxes such as oxydiacetic acid (diglycolic acid) are added to silver paste containing silver fine particles as a bonding material that can bond bonded objects together in an inert atmosphere without applying pressure between the bonded objects.
  • a bonding material to which components are added has been proposed (see, for example, JP 2011-240406 A).
  • the present invention uses a bonding material that can be easily printed on the objects to be bonded and can suppress generation of voids at the bonding portion between the objects to be bonded.
  • An object is to provide a joining method.
  • the bonding material consisting of the above, the content of silver fine particles is 5 to 30% by mass, the content of silver particles is 60 to 90% by mass, and the total content of silver fine particles and silver particles is 90% by mass or more, Discovered that it is possible to provide a bonding material and a bonding method using the same, which can be easily printed on the objects to be bonded and can suppress the generation of voids at the bonded portions of the objects to be bonded. It came to do. That is, the bonding material according to the present invention is a bonding material comprising silver fine particles having an average primary particle diameter of 1 to 50 nm, silver particles having an average primary particle diameter of 0.5 to 4 ⁇ m, a silver paste containing a solvent and a dispersant.
  • the content is 5 to 30% by mass, the content of silver particles is 60 to 90% by mass, and the total content of silver fine particles and silver particles is 90% by mass or more.
  • the dispersant is preferably composed of an acid dispersant and a phosphate ester dispersant.
  • the amount of the phosphate ester dispersant is preferably 0.01 to 0.1% by mass with respect to the silver paste, and the amount of the acid dispersant is 0.5 to 2% by mass with respect to the silver paste.
  • the silver paste preferably contains a sintering aid such as diglycolic acid, and the amount of the sintering aid is preferably 0.01 to 0.1% by mass with respect to the silver paste.
  • the solvent is preferably composed of alcohol and triol.
  • the silver fine particles are preferably coated with an organic compound having 8 or less carbon atoms such as hexanoic acid, and the silver particles are preferably coated with an organic compound such as oleic acid.
  • the silver in the bonding material is sintered and the objects to be bonded are bonded to each other via the silver bonding layer.
  • the ratio of the area occupied by the void to the area of the joint surface is preferably less than 10%.
  • the viscosity of the bonding material is 100 Pa ⁇ s or less when measured at 6.4 rpm at 25 ° C. by a rheometer.
  • the bonding method according to the present invention includes the above-described bonding material interposed between the objects to be bonded, and heated to sinter the silver in the bonding material to form a silver bonding layer. It is characterized by joining joined objects.
  • average primary particle diameter of silver fine particles refers to an average value of primary particle diameters of silver fine particles obtained by transmission electron micrograph (TEM image), and “average primary particle diameter of silver particles”.
  • TEM image transmission electron micrograph
  • ADVANTAGE OF THE INVENTION According to this invention, it is easy to print on a to-be-joined object, and can suppress that a void generate
  • An embodiment of a bonding material according to the present invention is a bonding material comprising silver particles containing silver fine particles having an average primary particle diameter of 1 to 50 nm, silver particles having an average primary particle diameter of 0.5 to 4 ⁇ m, a solvent and a dispersant.
  • the content of fine particles is 5 to 30% by mass, the content of silver particles is 60 to 90% by mass, and the total content of silver fine particles and silver particles is 90% by mass or more.
  • the average primary particle diameter of the silver fine particles (silver nanoparticles) is 1 to 50 nm, preferably 5 to 40 nm, and more preferably 10 to 30 nm.
  • the silver fine particles are preferably coated with an organic compound having 8 or less carbon atoms such as hexanoic acid or sorbic acid, and more preferably coated with hexanoic acid.
  • the average primary particle diameter of silver particles is 0.5 to 4 ⁇ m, preferably 0.7 to 3.5 ⁇ m, and more preferably 0.8 to 3 ⁇ m.
  • the silver particles are preferably coated with an organic compound such as oleic acid or stearic acid, and more preferably coated with oleic acid.
  • the dispersant is preferably composed of an acid dispersant and a phosphate ester dispersant.
  • a dispersant containing a carboxyl group can be used, and it is preferable to use a dispersant containing a carboxyl group and having an ether structure.
  • a dispersant containing a phosphate ester can be used.
  • the amount of the acid-based dispersant is preferably 0.5 to 2% by mass, and more preferably 0.8 to 1.5% by mass with respect to the silver paste.
  • the amount of the phosphoric acid ester dispersant is preferably 0.01 to 0.1% by mass, more preferably 0.03 to 0.08% by mass with respect to the silver paste.
  • the silver paste preferably contains a sintering aid such as diglycolic acid as an additive.
  • the amount of the sintering aid is preferably 0.01 to 0.1% by mass, more preferably 0.05 to 0.07% by mass with respect to the silver paste.
  • the solvent is preferably composed of alcohol and triol, and 1-octanol, 1-decanol, and the like can be used as the alcohol.
  • the amount of alcohol is preferably 3 to 7% by mass, more preferably 4 to 6% by mass, based on the silver paste.
  • the amount of triol is preferably 0.3 to 1% by mass, more preferably 0.4 to 0.6% by mass with respect to the silver paste.
  • the ratio of the area occupied by voids to the area of the surface is preferably less than 10%.
  • the viscosity of the bonding material is preferably 100 Pa ⁇ s or less when the viscosity of the bonding material is measured at 6.4 rpm at 25 ° C. with a rheometer (viscoelasticity measuring device).
  • the above-mentioned bonding material is interposed between the objects to be bonded and heated, so that the silver in the bonding material is sintered to form a silver bonding layer.
  • the objects to be joined are joined together.
  • the bonding material is applied to at least one of the two objects to be bonded, arranged so that the bonding material is interposed between the objects to be bonded, and heated at 60 to 200 ° C., preferably 80 to 170 ° C.
  • the silver in the silver paste is sintered to form a silver bonding layer by heating at 210 to 400 ° C., preferably 230 to 300 ° C.
  • the objects to be joined are joined together by the silver joining layer. Note that it is not necessary to apply pressure between the objects to be bonded during heating, but pressure may be applied.
  • the objects to be bonded can be bonded to each other even when heated in an inert atmosphere such as a nitrogen atmosphere, but the objects to be bonded can be bonded to each other even under pressure in the air.
  • an inert atmosphere such as a nitrogen atmosphere
  • Ti1 (1 rpm viscosity / 5 viscosity) (hereinafter this Ti value is called "Ti1") ratio (2s viscosity / 20s viscosity -1) (Ti value of -1 in the viscosity of the 2s -1 for viscosity 20s -1 measured at 4, 25 ° C. is) (hereinafter, the Ti value Ti2 "hereinafter) is 6.5, printability (printability of the bonding material (silver paste)) was good.
  • a copper plate having a size of 10 mm ⁇ 10 mm ⁇ 1 mm treated with 10% sulfuric acid after degreasing with ethanol and an Si chip having a size of 3 mm ⁇ 3 mm ⁇ 0.3 mm subjected to Ag plating were prepared.
  • a metal mask having a thickness of 50 ⁇ m was placed on the copper plate, and the bonding material (silver paste) was applied on the copper plate so as to have a size of 3.5 mm ⁇ 3.5 mm and a thickness of 50 ⁇ m.
  • an Si chip is placed on the bonding material applied on the copper plate, a load of 0.1 MPa is applied between the bonding material and the Si chip for 10 seconds, and then the temperature is raised from 25 ° C. in a nitrogen atmosphere in a lamp furnace.
  • the silver paste is dried by heating up to 150 ° C. at a temperature rate of 0.1 ° C./s and pre-baking at 150 ° C. for 30 minutes, and then increased to 250 ° C. at a rate of temperature increase of 0.1 ° C./s.
  • the main baking was performed by heating and holding at 250 ° C. for 60 minutes to sinter the silver in the silver paste to form a silver bonding layer, and the Si chip was bonded to the copper plate by the silver bonding layer.
  • the void ratio of the bonded surface (the ratio of the area occupied by the void to the area of the bonded surface) was calculated from the X-ray photograph.
  • the void ratio was as low as 5.1%. It was good.
  • the shear strength force when the Si chip was pushed from the lateral direction and the Si chip was peeled off from the copper plate
  • the shear strength was as high as 11 MPa to be almost satisfactory. It was.
  • a bonding material made of the same silver paste as in Example 1 was prepared except that the amount of silver fine particles coated with hexanoic acid was 20% by mass and the amount of silver particles coated with oleic acid was 73% by mass.
  • the viscosity of this bonding material was determined in the same manner as in Example 1, it was 269.5 (Pa ⁇ s) at 0.6 rpm (2.1 s ⁇ 1 ) at 25 ° C. and 187.4 at 1 rpm.
  • a bonding material comprising the same silver paste as in Example 1 except that the amount of silver fine particles coated with hexanoic acid was 27.9% by mass and the amount of silver particles coated with oleic acid was 65.1% by mass. Prepared.
  • the viscosity of this bonding material was determined by the same method as in Example 1, it was 547.1 (Pa ⁇ s) at 0.6 rpm (2.1 s ⁇ 1 ) at 25 ° C. and 426 (Pa S) 222 rpm at 2 rpm, 83.37 Pas at 5 rpm, 55.49 Pa at 6.4 rpm (20.1 s ⁇ 1 ), 5 rpm measured at 25 ° C.
  • the ratio (Ti1) of the viscosity at 1 rpm to the viscosity of 5 is 5.1
  • the ratio of the viscosity of 2s- 1 to the viscosity of 20s- 1 measured at 25 ° C. (Ti2) is 9.9
  • the bonding material (silver paste) The printability (printability) of was good.
  • a bonded body was obtained in the same manner as in Example 1.
  • the void ratio of the joint surface was calculated by the same method as in Example 1 and the shear strength was measured. As a result, there was almost no void, the void ratio was very good at 0%, and the shear strength was It was as high as 32.6 MPa and was good.
  • a bonding material made of the same silver paste as in Example 1 was prepared except that the amount of silver fine particles coated with hexanoic acid was 35% by mass and the amount of silver particles coated with oleic acid was 58% by mass.
  • the viscosity of this bonding material was determined in the same manner as in Example 1, it was 1166 (Pa ⁇ s) at 0.6 rpm (2.1 s ⁇ 1 ) at 25 ° C. and 992.7 (Pa ⁇ s) at 1 rpm.
  • Comparative Example 1 A bonding material comprising the same silver paste as in Example 1 except that the amount of silver fine particles coated with hexanoic acid was 42.5% by mass and the amount of silver particles coated with oleic acid was 50.5% by mass. Prepared.
  • Comparative Example 2 A bonding material made of the same silver paste as in Example 1 was prepared except that the amount of silver fine particles coated with hexanoic acid was 50% by mass and the amount of silver particles coated with oleic acid was 43% by mass.
  • the viscosity of this bonding material (silver paste) was determined by the same method as in Example 1, the viscosity was too high to be measured, and the printing property (printability) of the bonding material (silver paste) was very poor.
  • a bonded body was obtained in the same manner as in Example 1. With respect to this joined body, the void ratio of the joint surface was calculated by the same method as in Example 1 and the shear strength was measured. The void ratio was as high as 11%, which was not good, but the shear strength was 33.3 MPa. It was high and good.
  • Example 2 was used except that instead of silver particles coated with oleic acid, 73% by mass of silver particles (AG5-7F manufactured by DOWA Hightech Co., Ltd.) having an average primary particle diameter of 3 ⁇ m coated with stearic acid was used. A bonding material made of the same silver paste was prepared. When the viscosity of this bonding material (silver paste) was determined by the same method as in Example 1, it was 85.91 (Pa ⁇ s) at 0.6 rpm (2.1 s ⁇ 1 ) at 25 ° C. and 58.41 at 1 rpm.
  • Example 2 Using this bonding material (silver paste), a bonded body was obtained in the same manner as in Example 1. With respect to this joined body, the void ratio of the joint surface was calculated by the same method as in Example 1 and the shear strength was measured. As a result, the void ratio was as low as 6.3% to some extent, and the shear strength was 29 MPa. It was high and good. Comparative Example 3 Example 2 was used except that 20% by mass of sorbic acid-coated silver fine particles having an average primary particle diameter of 60 nm (DP-2 manufactured by DOWA Electronics Co., Ltd.) was used instead of silver fine particles coated with hexanoic acid. A bonding material made of silver paste was prepared.
  • the ratio (Ti1) of the viscosity of 1 rpm to the viscosity of 5 rpm measured in step 4.3 is 4.3, and the ratio of the viscosity of 2s ⁇ 1 (Ti2) to the viscosity of 20 s ⁇ 1 measured at 25 ° C. is 7.8.
  • the printability (printability) of (silver paste) was good.
  • a bonded body was obtained in the same manner as in Example 1.
  • the void ratio of the joint surface was calculated by the same method as in Example 1 and the shear strength was measured.
  • the void ratio was as high as 20.7%, which was not good, but the shear strength was 20 It was 0.7 MPa, almost good.
  • a joining material made of the same silver paste as in Example 2 was prepared except that the amount of the phosphate ester dispersant was changed to 0.04% by mass.
  • the viscosity of this bonding material was 230.6 (Pa ⁇ s) at 0.6 rpm (2.1 s ⁇ 1 ) at 25 ° C. and 372.8 at 1 rpm.
  • (Pa ⁇ s) 255.3 (Pa ⁇ s) at 2 rpm, 114.2 (Pa ⁇ s) at 5 rpm, 57.31 (Pa ⁇ s) at 6.4 rpm (20.1 s ⁇ 1 ), 25 ° C.
  • the ratio of the viscosity of 1 rpm to the viscosity of 5 rpm measured at 5 (Ti1) is 3.3, and the ratio of the viscosity of 2s ⁇ 1 to the viscosity of 20 s ⁇ 1 measured at 25 ° C. (Ti2) is 4.0.
  • the printability (printability) of (silver paste) was good. Using this bonding material (silver paste), a bonded body was obtained in the same manner as in Example 1. About this joined body, the void ratio of the joint surface was calculated by the same method as in Example 1 and the shear strength was measured.
  • Comparative Example 4 A bonding material made of the same silver paste as in Example 2 was prepared except that the amount of the phosphate ester dispersant was 1% by mass and the acid dispersant was not added. When the viscosity of this bonding material (silver paste) was determined by the same method as in Example 1, it was 15.58 (Pa ⁇ s) at 25 rpm and 0.6 rpm (2.1 s ⁇ 1 ), and 10.85 at 1 rpm.
  • Example 2 Using this bonding material (silver paste), a bonded body was obtained in the same manner as in Example 1.
  • the void ratio of the joint surface was calculated by the same method as in Example 1 and the shear strength was measured.
  • the void ratio was as high as 25.8%, which was not good, but the shear strength was 26. It was as high as 3 MPa and was good.
  • a bonding material made of the same silver paste as in Example 2 was prepared except that 5.353 mass% of 1-octanol was used instead of 1-decanol as the alcohol solvent.
  • the viscosity of the bonding material was determined in the same manner as in Example 1, it was 303.7 at 25 rpm and 0.6 rpm (2.1 s ⁇ 1 ) at 30 rpm (27 ⁇ 1).
  • the ratio of the viscosity of 1 rpm to the viscosity of 5 rpm (Ti1) was 4.1
  • the ratio of the viscosity of 2s- 1 to the viscosity of 20s- 1 measured at 25 ° C. (Ti2) was 6.2
  • the bonding material silver The printability (printability) of the paste
  • a bonded body was obtained in the same manner as in Example 1.
  • the void ratio of the joint surface was calculated by the same method as in Example 1 and the shear strength was measured. As a result, there was almost no void, the void ratio was very good at 0%, and the shear strength was It was as high as 28.4 MPa.
  • the void ratio of the joint surface was calculated by the same method as in Example 1 and the shear strength was measured. As a result, there was almost no void, the void ratio was very good at 0%, and the shear strength was It was as high as 49.7 MPa and was good.
  • the amount of silver fine particles coated with hexanoic acid is 20.108% by mass
  • the amount of silver particles coated with oleic acid is 73.392% by mass
  • diglycolic acid (DGA) as a baking aid (additive) The amount of dicarboxylic acid) is 0.062% by mass
  • the amount of acid dispersant is 0.929% by mass
  • the amount of phosphate ester dispersant is 0.074% by mass
  • the amount of triol as a solvent is 0.464% by mass.
  • the void ratio of the joint surface was calculated by the same method as in Example 1 and the shear strength was measured. As a result, there was almost no void, the void ratio was very good at 0%, and the shear strength was It was as high as 78.1 MPa.
  • the amount of silver fine particles coated with hexanoic acid was 20.215% by mass, the amount of silver particles coated with oleic acid was 73.785% by mass, and diglycolic acid (DGA) as a baking aid (additive)
  • DGA diglycolic acid
  • the amount of dicarboxylic acid is 0.057% by mass, the amount of acid dispersant is 0.857% by mass, the amount of phosphate ester dispersant is 0.069% by mass, and the amount of triol as a solvent is 0.429% by mass.
  • the void ratio of the joint surface was calculated by the same method as in Example 1 and the shear strength was measured. As a result, there was almost no void, the void ratio was very good at 0%, and the shear strength was It was as high as 26.6 MPa and was good.
  • Tables 1 to 4 show the manufacturing conditions and characteristics of the bonding materials of these examples and comparative examples. In Table 4, the case where the viscosity of the bonding material, the printability, and the void ratio of the bonding surface are good is indicated by “ ⁇ ”, and the case where it is not good is indicated by “X”.

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  • Chemical & Material Sciences (AREA)
  • Nanotechnology (AREA)
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  • Inorganic Chemistry (AREA)
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Abstract

A joining material consisting essentially of a silver paste which comprises silver nanoparticles that are coated with hexanoic acid or other organic compound having at most 8 carbon atoms and that have a mean primary particle diameter of 1 to 50nm, silver micro- particles that are coated with an organic compound such as oleic acid and that have a mean primary particle diameter of 0.5 to 4μm, a solvent consisting of 3 to 7 mass% of an alcohol and 0.3 to 1 mass% of a triol, a dispersant consisting of 0.5 to 2 mass% of an acid-based dispersant and 0.01 to 0.1 mass% of a phosphate ester-based dispersant, and 0.01 to 0.1 mass% of a sintering aid such as diglycolic acid, wherein: the content of the silver nanoparticles is 5 to 30 mass%; the content of the silver microparticles is 60 to 90 mass%; and the total content of the silver nanoparticles and the silver microparticles is 90 mass% or more.

Description

接合材およびそれを用いた接合方法Bonding material and bonding method using the same
　本発明は、接合材およびそれを用いた接合方法に関し、特に、銀微粒子を含む銀ペーストからなる接合材およびそれを用いて被接合物同士を接合する方法に関する。 The present invention relates to a bonding material and a bonding method using the same, and more particularly to a bonding material made of a silver paste containing silver fine particles and a method for bonding objects to be bonded together using the bonding material.
　近年、銀微粒子を含む銀ペーストを接合材として使用し、被接合物間に接合材を介在させ、被接合物間に圧力を加えながら所定時間加熱して、接合材中の銀を焼結させて、被接合物同士を接合することが提案されている（例えば、特開２０１１−８０１４７号公報参照）。
　このような接合材を鉛はんだの代わりに使用して被接合物同士を接合するためには、鉛はんだにより被接合物同士を接合する場合と同様に、被接合物間に圧力を加えないで接合（無加圧接合）することができるのが好ましい。また、被接合物間の接合部に酸化銀が形成されて接合力が低下するのを防止するために、窒素雰囲気などの不活性雰囲気中でも被接合物同士を接合することができるのが好ましい。
　このように被接合物間に圧力を加えなくても不活性雰囲気中で被接合物同士を接合することができる接合材として、銀微粒子を含む銀ペーストにオキシジ酢酸（ジグリコール酸）などのフラックス成分を添加した接合材が提案されている（例えば、特開２０１１−２４０４０６号公報参照）。
　また、接合材により被接合物同士を接合した際に接合面にボイドが存在すると、被接合物同士が所望の接合力で接合していたとしても、繰り返しの冷熱サイクル（例えば、−５５~１５０℃で５００回以上繰り返される冷熱サイクル）が加えられると、ボイドの部分に応力が加わって、ボイドから接合層に亀裂が入り、接合の信頼性に欠ける。そのため、接合材により被接合物同士を良好に接合するためには、接合部にボイドが発生するのを抑える（接合面の面積に対するボイドが占める面積の割合（ボイド率）を１０％未満に抑える）必要があり、ボイドの要因となる溶剤（銀微粒子の分散媒）の添加量を抑える（銀の含有量を高くする）必要がある。一方、メタルマスクを使用してスクリーン印刷により接合材を良好に塗布するためには、接合材の粘度を下げる必要がある。しかし、接合材の粘度を下げると接合材中の銀の含有量が低下し、一方、接合材中の銀の含有量を高くすると接合材の粘度が高くなり、接合材の粘度と接合材中の銀の含有量はトレードオフの関係にある。
　一般に、銀微粒子を含む銀ペーストからなる接合材の粘度を下げるためには、接合材に分散剤を添加することが知られており、銀の含有量が高く（溶剤の添加量が低く）且つ印刷に適した粘度に下げることができる接合材として、銀微粒子を含む銀ペーストにリン酸エステル系分散剤などのリン酸系分散剤を添加した接合材が提案されている（例えば、特開２０１３−４３０９号公報参照）。
　しかし、リン酸エステル系分散剤などのリン酸系分散剤を添加した接合材により被接合物間を接合すると、接合部にボイドが発生し易くなる。 In recent years, silver paste containing silver fine particles has been used as a bonding material, the bonding material is interposed between the objects to be bonded, and heated for a predetermined time while applying pressure between the objects to be bonded to sinter the silver in the bonding material. Thus, it has been proposed to join objects to be joined (see, for example, JP 2011-80147 A).
In order to join objects to be joined using such a joining material instead of lead solder, do not apply pressure between the objects to be joined as in the case of joining objects to be joined with lead solder. It is preferable that bonding (pressureless bonding) can be performed. In addition, in order to prevent silver oxide from being formed at the joint between the objects to be bonded and the bonding force from being lowered, it is preferable that the objects to be bonded can be bonded even in an inert atmosphere such as a nitrogen atmosphere.
In this way, fluxes such as oxydiacetic acid (diglycolic acid) are added to silver paste containing silver fine particles as a bonding material that can bond bonded objects together in an inert atmosphere without applying pressure between the bonded objects. A bonding material to which components are added has been proposed (see, for example, JP 2011-240406 A).
In addition, when voids are present on the bonding surfaces when the objects to be bonded are bonded with the bonding material, even if the objects to be bonded are bonded with a desired bonding force, repeated cooling and heating cycles (for example, −55 to 150). When a thermal cycle that is repeated 500 times or more at 0 ° C. is applied, stress is applied to the void portion, and the bonding layer cracks from the void, resulting in poor reliability of bonding. Therefore, in order to satisfactorily bond the objects to be bonded together with the bonding material, generation of voids in the bonded portion is suppressed (the ratio of the area occupied by voids to the bonded area (void ratio) is suppressed to less than 10%. It is necessary to suppress the amount of the solvent (dispersion medium for silver fine particles) that causes voids (to increase the silver content). On the other hand, in order to satisfactorily apply the bonding material by screen printing using a metal mask, it is necessary to reduce the viscosity of the bonding material. However, lowering the viscosity of the bonding material decreases the silver content in the bonding material, while increasing the silver content in the bonding material increases the viscosity of the bonding material. The silver content is in a trade-off relationship.
In general, it is known to add a dispersant to the bonding material in order to lower the viscosity of the bonding material made of silver paste containing silver fine particles, and the silver content is high (the addition amount of the solvent is low) and As a bonding material that can be reduced to a viscosity suitable for printing, a bonding material in which a phosphoric acid dispersant such as a phosphoric acid ester dispersing agent is added to a silver paste containing silver fine particles has been proposed (for example, Japanese Patent Laid-Open No. 2013-2001). -4309).
However, if the objects to be joined are joined with a joining material to which a phosphate dispersant such as a phosphate ester dispersant is added, voids are likely to be generated at the joint.
　したがって、本発明は、上述した従来の問題点に鑑み、被接合物に印刷し易く且つ被接合物同士の接合部にボイドが発生するのを抑制することができる、接合材およびそれを用いた接合方法を提供することを目的とする。
　本発明者らは、上記課題を解決するために鋭意研究した結果、平均一次粒子径１~５０ｎｍの銀微粒子と平均一次粒子径０．５~４μｍの銀粒子と溶剤と分散剤を含む銀ペーストからなる接合材において、銀微粒子の含有量を５~３０質量％、銀粒子の含有量を６０~９０質量％、銀微粒子と銀粒子の合計の含有量を９０質量％以上にすることにより、被接合物に印刷し易く且つ被接合物同士の接合部にボイドが発生するのを抑制することができる、接合材およびそれを用いた接合方法を提供することができることを見出し、本発明を完成するに至った。
　すなわち、本発明による接合材は、平均一次粒子径１~５０ｎｍの銀微粒子と平均一次粒子径０．５~４μｍの銀粒子と溶剤と分散剤を含む銀ペーストからなる接合材において、銀微粒子の含有量が５~３０質量％、銀粒子の含有量が６０~９０質量％、銀微粒子と銀粒子の合計の含有量が９０質量％以上であることを特徴とする。
　この接合材において、分散剤が酸系分散剤とリン酸エステル系分散剤とからなるのが好ましい。リン酸エステル系分散剤の量は銀ペーストに対して０．０１~０．１質量％であるのが好ましく、酸系分散剤の量は銀ペーストに対して０．５~２質量％であるのが好ましい。また、銀ペーストがジグリコール酸などの焼結助剤を含むのが好ましく、焼結助剤の量は銀ペーストに対して０．０１~０．１質量％であるのが好ましい。また、溶剤がアルコールとトリオールとからなるのが好ましい。さらに、銀微粒子がヘキサン酸などの炭素数８以下の有機化合物で被覆されているのが好ましく、銀粒子がオレイン酸などの有機化合物で被覆されているのが好ましい。
　また、上記の接合材を被接合物間に介在させて加熱することにより、接合材中の銀を焼結させて銀接合層を介して被接合物同士を接合したときに、銀接合層の接合面の面積に対してボイドが占める面積の割合が１０％未満であるのが好ましい。また、上記の接合材の粘度をレオメーターにより２５℃において６．４ｒｐｍで測定したときの粘度が１００Ｐａ・ｓ以下であるのが好ましい。
　また、本発明による接合方法は、上記の接合材を被接合物間に介在させて加熱することにより、接合材中の銀を焼結させて銀接合層を形成し、この銀接合層により被接合物同士を接合することを特徴とする。
　なお、本明細書中において、「銀微粒子の平均一次粒子径」とは、透過型電子顕微鏡写真（ＴＥＭ像）による銀微粒子の一次粒子径の平均値をいい、「銀粒子の平均一次粒子径」とは、レーザー回折法により測定した銀粒子の５０％粒径（Ｄ５０径）（累積５０質量％粒径）をいう。
　本発明によれば、被接合物に印刷し易く且つ被接合物同士の接合部にボイドが発生するのを抑制することができる、接合材およびそれを用いた接合方法を提供することができる。 Therefore, in view of the above-described conventional problems, the present invention uses a bonding material that can be easily printed on the objects to be bonded and can suppress generation of voids at the bonding portion between the objects to be bonded. An object is to provide a joining method.
As a result of intensive studies to solve the above problems, the present inventors have found that a silver paste containing silver fine particles having an average primary particle diameter of 1 to 50 nm, silver particles having an average primary particle diameter of 0.5 to 4 μm, a solvent, and a dispersant. In the bonding material consisting of the above, the content of silver fine particles is 5 to 30% by mass, the content of silver particles is 60 to 90% by mass, and the total content of silver fine particles and silver particles is 90% by mass or more, Discovered that it is possible to provide a bonding material and a bonding method using the same, which can be easily printed on the objects to be bonded and can suppress the generation of voids at the bonded portions of the objects to be bonded. It came to do.
That is, the bonding material according to the present invention is a bonding material comprising silver fine particles having an average primary particle diameter of 1 to 50 nm, silver particles having an average primary particle diameter of 0.5 to 4 μm, a silver paste containing a solvent and a dispersant. The content is 5 to 30% by mass, the content of silver particles is 60 to 90% by mass, and the total content of silver fine particles and silver particles is 90% by mass or more.
In this bonding material, the dispersant is preferably composed of an acid dispersant and a phosphate ester dispersant. The amount of the phosphate ester dispersant is preferably 0.01 to 0.1% by mass with respect to the silver paste, and the amount of the acid dispersant is 0.5 to 2% by mass with respect to the silver paste. Is preferred. The silver paste preferably contains a sintering aid such as diglycolic acid, and the amount of the sintering aid is preferably 0.01 to 0.1% by mass with respect to the silver paste. The solvent is preferably composed of alcohol and triol. Further, the silver fine particles are preferably coated with an organic compound having 8 or less carbon atoms such as hexanoic acid, and the silver particles are preferably coated with an organic compound such as oleic acid.
In addition, when the above-mentioned bonding material is interposed between the objects to be bonded and heated, the silver in the bonding material is sintered and the objects to be bonded are bonded to each other via the silver bonding layer. The ratio of the area occupied by the void to the area of the joint surface is preferably less than 10%. Moreover, it is preferable that the viscosity of the bonding material is 100 Pa · s or less when measured at 6.4 rpm at 25 ° C. by a rheometer.
Further, the bonding method according to the present invention includes the above-described bonding material interposed between the objects to be bonded, and heated to sinter the silver in the bonding material to form a silver bonding layer. It is characterized by joining joined objects.
In the present specification, “average primary particle diameter of silver fine particles” refers to an average value of primary particle diameters of silver fine particles obtained by transmission electron micrograph (TEM image), and “average primary particle diameter of silver particles”. "Means 50% particle diameter (D 50 diameter) (cumulative 50 mass% particle diameter) of silver particles measured by a laser diffraction method.
ADVANTAGE OF THE INVENTION According to this invention, it is easy to print on a to-be-joined object, and can suppress that a void generate | occur | produces in the junction part of to-be-joined objects, and the joining method using the same can be provided.
　本発明による接合材の実施の形態は、平均一次粒子径１~５０ｎｍの銀微粒子と平均一次粒子径０．５~４μｍの銀粒子と溶剤と分散剤を含む銀ペーストからなる接合材において、銀微粒子の含有量が５~３０質量％、銀粒子の含有量が６０~９０質量％、銀微粒子と銀粒子の合計の含有量が９０質量％以上である。
　銀微粒子（銀ナノ粒子）の平均一次粒子径は、１~５０ｎｍであり、５~４０ｎｍであるのが好ましく、１０~３０ｎｍであるのがさらに好ましい。また、銀微粒子がヘキサン酸やソルビン酸などの炭素数８以下の有機化合物で被覆されているのが好ましく、ヘキサン酸で被覆されているのがさらに好ましい。
　銀粒子（銀ミクロン粒子）の平均一次粒子径は、０．５~４μｍであり、０．７~３．５μｍであるのが好ましく、０．８~３μｍであるのがさらに好ましい。また、銀粒子がオレイン酸やステアリン酸などの有機化合物で被覆されているのが好ましく、オレイン酸で被覆されているのがさらに好ましい。
　分散剤は、酸系分散剤とリン酸エステル系分散剤とからなるのが好ましい。酸系分散剤として、カルボキシル基を含むなどの分散剤を使用することができ、カルボキシル基を含み且つエーテル構造を有する分散剤を使用するのが好ましい。リン酸エステル系分散剤として、リン酸エステルを含む分散剤を使用することができる。酸系分散剤の量は、銀ペーストに対して０．５~２質量％であるのが好ましく、０．８~１．５質量％であるのがさらに好ましい。リン酸エステル系分散剤の量は、銀ペーストに対して０．０１~０．１質量％であるのが好ましく、０．０３~０．０８質量％であるのがさらに好ましい。
　銀ペーストは、添加剤としてジグリコール酸などの焼結助剤を含むのが好ましい。焼結助剤の量は、銀ペーストに対して０．０１~０．１質量％であるのが好ましく、０．０５~０．０７質量％であるのがさらに好ましい。
　溶剤は、アルコールとトリオールとからなるのが好ましく、アルコールとして、１−オクタノールや１−デカノールなどを使用することができる。アルコールの量は、銀ペーストに対して３~７質量％であるのが好ましく、４~６質量％であるのがさらに好ましい。トリオールの量は、銀ペーストに対して０．３~１質量％であるのが好ましく、０．４~０．６質量％であるのがさらに好ましい。
　また、この接合材を被接合物間に介在させて加熱することにより、接合材中の銀を焼結させて銀接合層を介して被接合物同士を接合したときに、銀接合層の接合面の面積に対してボイドが占める面積の割合が１０％未満であるのが好ましい。
　また、この接合材の粘度をレオメーター（粘弾性測定装置）により２５℃において６．４ｒｐｍで測定したときの粘度が１００Ｐａ・ｓ以下であるのが好ましい。
　本発明による接合方法の実施の形態では、上記の接合材を被接合物間に介在させて加熱することにより、接合材中の銀を焼結させて銀接合層を形成し、この銀接合層により被接合物同士を接合する。
　具体的には、上記の接合材を２つの被接合物の少なくとも一方に塗布し、接合材が被接合物間に介在するように配置させ、６０~２００℃、好ましくは８０~１７０℃で加熱することにより接合材を乾燥させて予備乾燥膜を形成した後、２１０~４００℃、好ましくは２３０~３００℃で加熱することにより、銀ペースト中の銀を焼結させて銀接合層を形成し、この銀接合層によって被接合物同士を接合する。なお、加熱の際に、被接合物間に圧力を加える必要はないが、圧力を加えてもよい。また、窒素雰囲気などの不活性雰囲気中で加熱しても、被接合物同士を接合することができるが、大気中で加圧しても、被接合物同士を接合することができる。
　以下、本発明による接合材およびそれを用いた接合方法の実施例について詳細に説明する。 An embodiment of a bonding material according to the present invention is a bonding material comprising silver particles containing silver fine particles having an average primary particle diameter of 1 to 50 nm, silver particles having an average primary particle diameter of 0.5 to 4 μm, a solvent and a dispersant. The content of fine particles is 5 to 30% by mass, the content of silver particles is 60 to 90% by mass, and the total content of silver fine particles and silver particles is 90% by mass or more.
The average primary particle diameter of the silver fine particles (silver nanoparticles) is 1 to 50 nm, preferably 5 to 40 nm, and more preferably 10 to 30 nm. The silver fine particles are preferably coated with an organic compound having 8 or less carbon atoms such as hexanoic acid or sorbic acid, and more preferably coated with hexanoic acid.
The average primary particle diameter of silver particles (silver micron particles) is 0.5 to 4 μm, preferably 0.7 to 3.5 μm, and more preferably 0.8 to 3 μm. The silver particles are preferably coated with an organic compound such as oleic acid or stearic acid, and more preferably coated with oleic acid.
The dispersant is preferably composed of an acid dispersant and a phosphate ester dispersant. As the acid dispersant, a dispersant containing a carboxyl group can be used, and it is preferable to use a dispersant containing a carboxyl group and having an ether structure. As the phosphate ester dispersant, a dispersant containing a phosphate ester can be used. The amount of the acid-based dispersant is preferably 0.5 to 2% by mass, and more preferably 0.8 to 1.5% by mass with respect to the silver paste. The amount of the phosphoric acid ester dispersant is preferably 0.01 to 0.1% by mass, more preferably 0.03 to 0.08% by mass with respect to the silver paste.
The silver paste preferably contains a sintering aid such as diglycolic acid as an additive. The amount of the sintering aid is preferably 0.01 to 0.1% by mass, more preferably 0.05 to 0.07% by mass with respect to the silver paste.
The solvent is preferably composed of alcohol and triol, and 1-octanol, 1-decanol, and the like can be used as the alcohol. The amount of alcohol is preferably 3 to 7% by mass, more preferably 4 to 6% by mass, based on the silver paste. The amount of triol is preferably 0.3 to 1% by mass, more preferably 0.4 to 0.6% by mass with respect to the silver paste.
In addition, when the joining material is interposed between the objects to be joined and heated, the silver in the joining material is sintered and the objects to be joined are joined together via the silver joining layer. The ratio of the area occupied by voids to the area of the surface is preferably less than 10%.
The viscosity of the bonding material is preferably 100 Pa · s or less when the viscosity of the bonding material is measured at 6.4 rpm at 25 ° C. with a rheometer (viscoelasticity measuring device).
In the embodiment of the bonding method according to the present invention, the above-mentioned bonding material is interposed between the objects to be bonded and heated, so that the silver in the bonding material is sintered to form a silver bonding layer. The objects to be joined are joined together.
Specifically, the bonding material is applied to at least one of the two objects to be bonded, arranged so that the bonding material is interposed between the objects to be bonded, and heated at 60 to 200 ° C., preferably 80 to 170 ° C. After drying the bonding material to form a pre-dried film, the silver in the silver paste is sintered to form a silver bonding layer by heating at 210 to 400 ° C., preferably 230 to 300 ° C. The objects to be joined are joined together by the silver joining layer. Note that it is not necessary to apply pressure between the objects to be bonded during heating, but pressure may be applied. Further, the objects to be bonded can be bonded to each other even when heated in an inert atmosphere such as a nitrogen atmosphere, but the objects to be bonded can be bonded to each other even under pressure in the air.
Hereinafter, examples of the bonding material and the bonding method using the same according to the present invention will be described in detail.
　ヘキサン酸で被覆された平均一次粒子径２０ｎｍの銀微粒子（ＤＯＷＡエレクトロニクス株式会社製のＤＰ−１）９．３質量％と、オレイン酸で被覆された平均一次粒子径０．８μｍの銀粒子（ＤＯＷＡハイテック株式会社製のＡＧ２−１Ｃ）８３．７質量％と、焼成助剤（添加剤）としてのジグリコール酸（ＤＧＡ）（ジカルボン酸）０．０６７質量％と、酸系分散剤（三洋化成工業株式会社製のビューライトＬＣＡ−２５ＮＨ）（非リン酸エステル系分散剤）１質量％と、リン酸エステル系分散剤（Ｌｕｂｒｉｚｏｌ社製のＳＯＬＰＬＵＳ　Ｄ５４０）０．０８質量％と、溶剤としての１−デカノール（アルコール）５．３５３質量％およびトリオール（日本テルペン化学株式会社製のＩＰＴＬ−Ａ）０．５質量％とを含む銀ペーストからなる接合材を用意した。
　この接合材（銀ペースト）の粘度をレオメーター（粘弾性測定装置）（Ｔｈｅｒｍｏ社製のＨＡＡＫＥ　Ｒｈｅｏｓｔｒｅｓｓ　６００、使用コーン：Ｃ３５／２°）により求めたところ、２５℃において０．６ｒｐｍ（２．１ｓ−１）で２０２．９（Ｐａ・ｓ）、１ｒｐｍで１５０．５（Ｐａ・ｓ）、２ｒｐｍで８２．９２（Ｐａ・ｓ）、５ｒｐｍで３７．７１（Ｐａ・ｓ）、６．４ｒｐｍ（２０．１ｓ−１）で３０．９８（Ｐａ・ｓ）、２５℃で測定した５ｒｐｍの粘度に対する１ｒｐｍの粘度の比（１ｒｐｍの粘度／５ｒｐｍの粘度）（Ｔｉ値）（以下、このＴｉ値を「Ｔｉ１」という）は４、２５℃で測定した２０ｓ−１の粘度に対する２ｓ−１の粘度の比（２ｓ−１の粘度／２０ｓ−１の粘度）（Ｔｉ値）（以下、このＴｉ値を「Ｔｉ２」という）は６．５であり、接合材（銀ペースト）の印刷性（印刷適性）は良好であった。
　また、エタノールで脱脂した後に１０％硫酸で処理した１０ｍｍ×１０ｍｍ×１ｍｍの大きさの銅板と、Ａｇめっきを施した３ｍｍ×３ｍｍ×０．３ｍｍの大きさのＳｉチップを用意した。
　次に、銅板上に厚さ５０μｍのメタルマスクを配置し、上記の接合材（銀ペースト）を３．５ｍｍ×３．５ｍｍの大きさで厚さ５０μｍになるように銅板上に塗布した。
　次に、銅板上に塗布された接合材上にＳｉチップを配置し、接合材とＳｉチップの間に０．１ＭＰａの荷重を１０秒間かけた後、ランプ炉により窒素雰囲気中において２５℃から昇温速度０．１℃／ｓで１５０℃まで昇温させ、１５０℃で３０分間保持する予備焼成を行って銀ペーストを乾燥させ、その後、昇温速度０．１℃／ｓで２５０℃まで昇温させ、２５０℃で６０分間保持する本焼成を行って、銀ペースト中の銀を焼結させて銀接合層を形成し、この銀接合層によってＳｉチップを銅板に接合した。
　このようにして得られた接合体について、Ｘ線写真から接合面のボイド率（接合面の面積に対してボイドが占める面積の割合）を算出したところ、ボイド率は５．１％と低く、良好であった。また、ボンドテスター（Ｄａｇｅ社製のシリーズ４０００）によりシア強度（Ｓｉチップを横方向から押してＳｉチップが銅板から剥がれたときの力）を測定したところ、シア強度は１１ＭＰａある程度高く、ほぼ良好であった。 9.3% by mass of silver fine particles (DP-1 manufactured by DOWA Electronics Co., Ltd.) with an average primary particle diameter of 20 nm coated with hexanoic acid, and silver particles (DOWA with an average primary particle diameter of 0.8 μm coated with oleic acid) AG2-1C manufactured by Hitech Co., Ltd. 83.7% by mass, diglycolic acid (DGA) (dicarboxylic acid) 0.067% by mass as a baking aid (additive), and acid-based dispersant (Sanyo Chemical Industries) 1% by weight of Viewlite LCA-25NH (non-phosphate ester dispersant) manufactured by Co., Ltd., 0.08% by mass of phosphate ester dispersant (SOLPLUS D540 manufactured by Lubrizol), and 1- From a silver paste containing decanol (alcohol) 5.353 mass% and triol (IPTL-A manufactured by Nippon Terpene Chemical Co., Ltd.) 0.5 mass% That was prepared with the bonding material.
When the viscosity of the bonding material (silver paste) was determined by a rheometer (viscoelasticity measuring device) (HAAKE Rheoless 600 manufactured by Thermo, cone used: C35 / 2 °), it was 0.6 rpm (2.1 s at 25 ° C). -1 ) 202.9 (Pa · s) at 1 rpm, 150.5 (Pa · s), 2 rpm at 82.92 (Pa · s), 5 rpm at 37.71 (Pa · s), 6.4 rpm ( 20.1 s −1 ) 30.98 (Pa · s), the ratio of the viscosity of 1 rpm to the viscosity of 5 rpm measured at 25 ° C. (1 rpm viscosity / 5 viscosity) (Ti value) (hereinafter this Ti value is called "Ti1") ratio (2s viscosity / 20s viscosity -1) (Ti value of -1 in the viscosity of the 2s -1 for viscosity 20s -1 measured at 4, 25 ° C. is) (hereinafter, the Ti value Ti2 "hereinafter) is 6.5, printability (printability of the bonding material (silver paste)) was good.
In addition, a copper plate having a size of 10 mm × 10 mm × 1 mm treated with 10% sulfuric acid after degreasing with ethanol and an Si chip having a size of 3 mm × 3 mm × 0.3 mm subjected to Ag plating were prepared.
Next, a metal mask having a thickness of 50 μm was placed on the copper plate, and the bonding material (silver paste) was applied on the copper plate so as to have a size of 3.5 mm × 3.5 mm and a thickness of 50 μm.
Next, an Si chip is placed on the bonding material applied on the copper plate, a load of 0.1 MPa is applied between the bonding material and the Si chip for 10 seconds, and then the temperature is raised from 25 ° C. in a nitrogen atmosphere in a lamp furnace. The silver paste is dried by heating up to 150 ° C. at a temperature rate of 0.1 ° C./s and pre-baking at 150 ° C. for 30 minutes, and then increased to 250 ° C. at a rate of temperature increase of 0.1 ° C./s. The main baking was performed by heating and holding at 250 ° C. for 60 minutes to sinter the silver in the silver paste to form a silver bonding layer, and the Si chip was bonded to the copper plate by the silver bonding layer.
For the bonded body thus obtained, the void ratio of the bonded surface (the ratio of the area occupied by the void to the area of the bonded surface) was calculated from the X-ray photograph. The void ratio was as low as 5.1%. It was good. Further, when the shear strength (force when the Si chip was pushed from the lateral direction and the Si chip was peeled off from the copper plate) was measured by a bond tester (series 4000 manufactured by Dage), the shear strength was as high as 11 MPa to be almost satisfactory. It was.
　ヘキサン酸で被覆された銀微粒子の量を２０質量％、オレイン酸で被覆された銀粒子の量を７３質量％とした以外は、実施例１と同様の銀ペーストからなる接合材を用意した。
　この接合材（銀ペースト）の粘度を実施例１と同様の方法により求めたところ、２５℃において０．６ｒｐｍ（２．１ｓ−１）で２６９．５（Ｐａ・ｓ）、１ｒｐｍで１８７．４（Ｐａ・ｓ）、２ｒｐｍで１０６．６（Ｐａ・ｓ）、５ｒｐｍで４３．３７（Ｐａ・ｓ）、６．４ｒｐｍ（２０．１ｓ−１）で３３．７（Ｐａ・ｓ）、２５℃で測定した５ｒｐｍの粘度に対する１ｒｐｍの粘度の比（Ｔｉ１）は４．１、２５℃で測定した２０ｓ−１の粘度に対する２ｓ−１の粘度の比（Ｔｉ２）は８であり、接合材（銀ペースト）の印刷性（印刷適性）は良好であった。
　この接合材（銀ペースト）を使用して、実施例１と同様の方法により接合体を得た。この接合体について、実施例１と同様の方法により、接合面のボイド率を算出し、シア強度を測定したところ、ボイド率は２．４％と低く、良好であり、シア強度は３１．７ＭＰａと高く、良好であった。 A bonding material made of the same silver paste as in Example 1 was prepared except that the amount of silver fine particles coated with hexanoic acid was 20% by mass and the amount of silver particles coated with oleic acid was 73% by mass.
When the viscosity of this bonding material (silver paste) was determined in the same manner as in Example 1, it was 269.5 (Pa · s) at 0.6 rpm (2.1 s −1 ) at 25 ° C. and 187.4 at 1 rpm. (Pa · s) 106.6 (Pa · s) at 2 rpm, 43.37 (Pa · s) at 5 rpm, 33.7 (Pa · s) at 6.4 rpm (20.1 s −1 ), 25 ° C. The ratio (Ti1) of the viscosity of 1 rpm to the viscosity of 5 rpm measured in step 4.1 is 4.1, the ratio of the viscosity of 2s −1 to the viscosity of 20 s −1 (Ti2) measured at 25 ° C. is 8, and the bonding material (silver The printability (printability) of the paste) was good.
Using this bonding material (silver paste), a bonded body was obtained in the same manner as in Example 1. With respect to this joined body, the void ratio of the joint surface was calculated by the same method as in Example 1 and the shear strength was measured. As a result, the void ratio was as low as 2.4%, and the shear strength was 31.7 MPa. It was high and good.
　ヘキサン酸で被覆された銀微粒子の量を２７．９質量％、オレイン酸で被覆された銀粒子の量を６５．１質量％とした以外は、実施例１と同様の銀ペーストからなる接合材を用意した。
　この接合材（銀ペースト）の粘度を実施例１と同様の方法により求めたところ、２５℃において０．６ｒｐｍ（２．１ｓ−１）で５４７．１（Ｐａ・ｓ）、１ｒｐｍで４２６（Ｐａ・ｓ）、２ｒｐｍで２２２（Ｐａ・ｓ）、５ｒｐｍで８３．３７（Ｐａ・ｓ）、６．４ｒｐｍ（２０．１ｓ−１）で５５．４９（Ｐａ・ｓ）、２５℃で測定した５ｒｐｍの粘度に対する１ｒｐｍの粘度の比（Ｔｉ１）は５．１、２５℃で測定した２０ｓ−１の粘度に対する２ｓ−１の粘度の比（Ｔｉ２）は９．９であり、接合材（銀ペースト）の印刷性（印刷適性）は良好であった。
　この接合材（銀ペースト）を使用して、実施例１と同様の方法により接合体を得た。この接合体について、実施例１と同様の方法により、接合面のボイド率を算出し、シア強度を測定したところ、ボイドが殆どなく、ボイド率は０％と非常に良好であり、シア強度は３２．６ＭＰａと高く、良好であった。 A bonding material comprising the same silver paste as in Example 1 except that the amount of silver fine particles coated with hexanoic acid was 27.9% by mass and the amount of silver particles coated with oleic acid was 65.1% by mass. Prepared.
When the viscosity of this bonding material (silver paste) was determined by the same method as in Example 1, it was 547.1 (Pa · s) at 0.6 rpm (2.1 s −1 ) at 25 ° C. and 426 (Pa S) 222 rpm at 2 rpm, 83.37 Pas at 5 rpm, 55.49 Pa at 6.4 rpm (20.1 s −1 ), 5 rpm measured at 25 ° C. The ratio (Ti1) of the viscosity at 1 rpm to the viscosity of 5 is 5.1, the ratio of the viscosity of 2s- 1 to the viscosity of 20s- 1 measured at 25 ° C. (Ti2) is 9.9, and the bonding material (silver paste) The printability (printability) of was good.
Using this bonding material (silver paste), a bonded body was obtained in the same manner as in Example 1. About this joined body, the void ratio of the joint surface was calculated by the same method as in Example 1 and the shear strength was measured. As a result, there was almost no void, the void ratio was very good at 0%, and the shear strength was It was as high as 32.6 MPa and was good.
　ヘキサン酸で被覆された銀微粒子の量を３５質量％、オレイン酸で被覆された銀粒子の量を５８質量％とした以外は、実施例１と同様の銀ペーストからなる接合材を用意した。
　この接合材（銀ペースト）の粘度を実施例１と同様の方法により求めたところ、２５℃において０．６ｒｐｍ（２．１ｓ−１）で１１６６（Ｐａ・ｓ）、１ｒｐｍで９９２．７（Ｐａ・ｓ）、２ｒｐｍで７９１．６（Ｐａ・ｓ）、５ｒｐｍで６５．８４（Ｐａ・ｓ）、６．４ｒｐｍ（２０．１ｓ−１）で５１．４（Ｐａ・ｓ）、２５℃で測定した５ｒｐｍの粘度に対する１ｒｐｍの粘度の比（Ｔｉ１）は１５．１、２５℃で測定した２０ｓ−１の粘度に対する２ｓ−１の粘度の比（Ｔｉ２）は２２．７であり、接合材（銀ペースト）の印刷性（印刷適性）は良好であった。
　この接合材（銀ペースト）を使用して、実施例１と同様の方法により接合体を得た。この接合体について、実施例１と同様の方法により、接合面のボイド率を算出し、シア強度を測定したところ、ボイドが殆どなく、ボイド率は０％と非常に良好であり、シア強度は４３．４ＭＰａと高く、良好であった。
比較例１
　ヘキサン酸で被覆された銀微粒子の量を４２．５質量％、オレイン酸で被覆された銀粒子の量を５０．５質量％とした以外は、実施例１と同様の銀ペーストからなる接合材を用意した。
　この接合材（銀ペースト）の粘度を実施例１と同様の方法により求めたところ、粘度が高過ぎて測定できず、接合材（銀ペースト）の印刷性（印刷適性）は非常に悪かった。
　この接合材（銀ペースト）を使用して、実施例１と同様の方法により接合体を得た。この接合体について、実施例１と同様の方法により、接合面のボイド率を算出し、シア強度を測定したところ、ボイドが殆どなく、ボイド率は０％と非常に良好であり、シア強度は２１．９ＭＰａと高く、良好であった。
比較例２
　ヘキサン酸で被覆された銀微粒子の量を５０質量％、オレイン酸で被覆された銀粒子の量を４３質量％とした以外は、実施例１と同様の銀ペーストからなる接合材を用意した。
　この接合材（銀ペースト）の粘度を実施例１と同様の方法により求めたところ、粘度が高過ぎて測定できず、接合材（銀ペースト）の印刷性（印刷適性）は非常に悪かった。
　この接合材（銀ペースト）を使用して、実施例１と同様の方法により接合体を得た。この接合体について、実施例１と同様の方法により、接合面のボイド率を算出し、シア強度を測定したところ、ボイド率は１１％と高く、良好ではなかったが、シア強度は３３．３ＭＰａと高く、良好であった。 A bonding material made of the same silver paste as in Example 1 was prepared except that the amount of silver fine particles coated with hexanoic acid was 35% by mass and the amount of silver particles coated with oleic acid was 58% by mass.
When the viscosity of this bonding material (silver paste) was determined in the same manner as in Example 1, it was 1166 (Pa · s) at 0.6 rpm (2.1 s −1 ) at 25 ° C. and 992.7 (Pa · s) at 1 rpm. S) 791.6 (Pa · s) at 2 rpm, 65.84 (Pa · s) at 5 rpm, 51.4 (Pa · s) at 6.4 rpm (20.1 s −1 ), measured at 25 ° C. The ratio of the viscosity of 1 rpm to the viscosity of 5 rpm (Ti1) was 15.1, the ratio of the viscosity of 2s −1 to the viscosity of 20 s −1 measured at 25 ° C. (Ti2) was 22.7, and the bonding material (silver The printability (printability) of the paste) was good.
Using this bonding material (silver paste), a bonded body was obtained in the same manner as in Example 1. About this joined body, the void ratio of the joint surface was calculated by the same method as in Example 1 and the shear strength was measured. As a result, there was almost no void, the void ratio was very good at 0%, and the shear strength was It was as high as 43.4 MPa.
Comparative Example 1
A bonding material comprising the same silver paste as in Example 1 except that the amount of silver fine particles coated with hexanoic acid was 42.5% by mass and the amount of silver particles coated with oleic acid was 50.5% by mass. Prepared.
When the viscosity of this bonding material (silver paste) was determined by the same method as in Example 1, the viscosity was too high to be measured, and the printing property (printability) of the bonding material (silver paste) was very poor.
Using this bonding material (silver paste), a bonded body was obtained in the same manner as in Example 1. About this joined body, the void ratio of the joint surface was calculated by the same method as in Example 1 and the shear strength was measured. As a result, there was almost no void, the void ratio was very good at 0%, and the shear strength was It was as high as 21.9 MPa and was good.
Comparative Example 2
A bonding material made of the same silver paste as in Example 1 was prepared except that the amount of silver fine particles coated with hexanoic acid was 50% by mass and the amount of silver particles coated with oleic acid was 43% by mass.
When the viscosity of this bonding material (silver paste) was determined by the same method as in Example 1, the viscosity was too high to be measured, and the printing property (printability) of the bonding material (silver paste) was very poor.
Using this bonding material (silver paste), a bonded body was obtained in the same manner as in Example 1. With respect to this joined body, the void ratio of the joint surface was calculated by the same method as in Example 1 and the shear strength was measured. The void ratio was as high as 11%, which was not good, but the shear strength was 33.3 MPa. It was high and good.
　オレイン酸で被覆された銀粒子の代わりに、ステアリン酸で被覆された平均一次粒子径３μｍの銀粒子（ＤＯＷＡハイテック株式会社製のＡＧ５−７Ｆ）７３質量％を使用した以外は、実施例２と同様の銀ペーストからなる接合材を用意した。
　この接合材（銀ペースト）の粘度を実施例１と同様の方法により求めたところ、２５℃において０．６ｒｐｍ（２．１ｓ−１）で８５．９１（Ｐａ・ｓ）、１ｒｐｍで５８．４１（Ｐａ・ｓ）、２ｒｐｍで３３．６（Ｐａ・ｓ）、５ｒｐｍで１７．６９（Ｐａ・ｓ）、６．４ｒｐｍ（２０．１ｓ−１）で１５．２３（Ｐａ・ｓ）、２５℃で測定した５ｒｐｍの粘度に対する１ｒｐｍの粘度の比（Ｔｉ１）は３．３、２５℃で測定した２０ｓ−１の粘度に対する２ｓ−１の粘度の比（Ｔｉ２）は５．６であり、接合材（銀ペースト）の印刷性（印刷適性）は良好であった。
　この接合材（銀ペースト）を使用して、実施例１と同様の方法により接合体を得た。この接合体について、実施例１と同様の方法により、接合面のボイド率を算出し、シア強度を測定したところ、ボイド率は６．３％とある程度低く、ほぼ良好であり、シア強度は２９ＭＰａと高く、良好であった。
比較例３
　ヘキサン酸で被覆された銀微粒子の代わりに、ソルビン酸被覆された平均一次粒子径６０ｎｍの銀微粒子（ＤＯＷＡエレクトロニクス株式会社製のＤＰ−２）２０質量％を使用した以外は、実施例２と同様の銀ペーストからなる接合材を用意した。
　この接合材（銀ペースト）の粘度を実施例１と同様の方法により求めたところ、２５℃において０．６ｒｐｍ（２．１ｓ−１）で１３２．６（Ｐａ・ｓ）、１ｒｐｍで８９．９５（Ｐａ・ｓ）、２ｒｐｍで４７．３５（Ｐａ・ｓ）、５ｒｐｍで２０．９７（Ｐａ・ｓ）、６．４ｒｐｍ（２０．１ｓ−１）で１６．９５（Ｐａ・ｓ）、２５℃で測定した５ｒｐｍの粘度に対する１ｒｐｍの粘度の比（Ｔｉ１）は４．３、２５℃で測定した２０ｓ−１の粘度に対する２ｓ−１の粘度の比（Ｔｉ２）は７．８であり、接合材（銀ペースト）の印刷性（印刷適性）は良好であった。
　この接合材（銀ペースト）を使用して、実施例１と同様の方法により接合体を得た。この接合体について、実施例１と同様の方法により、接合面のボイド率を算出し、シア強度を測定したところ、ボイド率は２０．７％と高く、良好ではなかったが、シア強度は２０．７ＭＰａであり、ほぼ良好であった。 Example 2 was used except that instead of silver particles coated with oleic acid, 73% by mass of silver particles (AG5-7F manufactured by DOWA Hightech Co., Ltd.) having an average primary particle diameter of 3 μm coated with stearic acid was used. A bonding material made of the same silver paste was prepared.
When the viscosity of this bonding material (silver paste) was determined by the same method as in Example 1, it was 85.91 (Pa · s) at 0.6 rpm (2.1 s −1 ) at 25 ° C. and 58.41 at 1 rpm. (Pa · s) 33.6 (Pa · s) at 2 rpm, 17.69 (Pa · s) at 5 rpm, 15.23 (Pa · s) at 6.4 rpm (20.1 s −1 ), 25 ° C. The ratio (Ti1) of the viscosity at 1 rpm to the viscosity at 5 rpm measured in step 3.3 is 3.3, and the ratio of the viscosity of 2s −1 (Ti2) to the viscosity of 20 s −1 measured at 25 ° C. is 5.6. The printability (printability) of (silver paste) was good.
Using this bonding material (silver paste), a bonded body was obtained in the same manner as in Example 1. With respect to this joined body, the void ratio of the joint surface was calculated by the same method as in Example 1 and the shear strength was measured. As a result, the void ratio was as low as 6.3% to some extent, and the shear strength was 29 MPa. It was high and good.
Comparative Example 3
Example 2 was used except that 20% by mass of sorbic acid-coated silver fine particles having an average primary particle diameter of 60 nm (DP-2 manufactured by DOWA Electronics Co., Ltd.) was used instead of silver fine particles coated with hexanoic acid. A bonding material made of silver paste was prepared.
When the viscosity of this bonding material (silver paste) was determined by the same method as in Example 1, 132.6 (Pa · s) at 25 rpm and 0.6 rpm (2.1 s −1 ) at 1 rpm and 89.95 at 1 rpm. (Pa · s) 47.35 (Pa · s) at 2 rpm, 20.97 (Pa · s) at 5 rpm, 16.95 (Pa · s) at 6.4 rpm (20.1 s −1 ), 25 ° C. The ratio (Ti1) of the viscosity of 1 rpm to the viscosity of 5 rpm measured in step 4.3 is 4.3, and the ratio of the viscosity of 2s −1 (Ti2) to the viscosity of 20 s −1 measured at 25 ° C. is 7.8. The printability (printability) of (silver paste) was good.
Using this bonding material (silver paste), a bonded body was obtained in the same manner as in Example 1. About this joined body, the void ratio of the joint surface was calculated by the same method as in Example 1 and the shear strength was measured. The void ratio was as high as 20.7%, which was not good, but the shear strength was 20 It was 0.7 MPa, almost good.
　リン酸エステル系分散剤の量を０．０４質量％にした以外は、実施例２と同様の銀ペーストからなる接合材を用意した。
　この接合材（銀ペースト）の粘度を実施例１と同様の方法により求めたところ、２５℃において０．６ｒｐｍ（２．１ｓ−１）で２３０．６（Ｐａ・ｓ）、１ｒｐｍで３７２．８（Ｐａ・ｓ）、２ｒｐｍで２５５．３（Ｐａ・ｓ）、５ｒｐｍで１１４．２（Ｐａ・ｓ）、６．４ｒｐｍ（２０．１ｓ−１）で５７．３１（Ｐａ・ｓ）、２５℃で測定した５ｒｐｍの粘度に対する１ｒｐｍの粘度の比（Ｔｉ１）は３．３、２５℃で測定した２０ｓ−１の粘度に対する２ｓ−１の粘度の比（Ｔｉ２）は４．０であり、接合材（銀ペースト）の印刷性（印刷適性）は良好であった。
　この接合材（銀ペースト）を使用して、実施例１と同様の方法により接合体を得た。この接合体について、実施例１と同様の方法により、接合面のボイド率を算出し、シア強度を測定したところ、ボイドが殆どなく、ボイド率は０％と非常に良好であり、シア強度は３４．１ＭＰａと高く、良好であった。
比較例４
　リン酸エステル系分散剤の量を１質量％とし、酸系分散剤を添加しなかった以外は、実施例２と同様の銀ペーストからなる接合材を用意した。
　この接合材（銀ペースト）の粘度を実施例１と同様の方法により求めたところ、２５℃において０．６ｒｐｍ（２．１ｓ−１）で１５．５８（Ｐａ・ｓ）、１ｒｐｍで１０．８５（Ｐａ・ｓ）、２ｒｐｍで６．４０８（Ｐａ・ｓ）、５ｒｐｍで３．４０５（Ｐａ・ｓ）、６．４ｒｐｍ（２０．１ｓ−１）で２．９０７（Ｐａ・ｓ）、２５℃で測定した５ｒｐｍの粘度に対する１ｒｐｍの粘度の比（Ｔｉ１）は３．２、２５℃で測定した２０ｓ−１の粘度に対する２ｓ−１の粘度の比（Ｔｉ２）は５．４であり、接合材（銀ペースト）の印刷性（印刷適性）は良好であった。
　この接合材（銀ペースト）を使用して、実施例１と同様の方法により接合体を得た。この接合体について、実施例１と同様の方法により、接合面のボイド率を算出し、シア強度を測定したところ、ボイド率は２５．８％と高く、良好ではなかったが、シア強度は２６．３ＭＰａと高く、良好であった。 A joining material made of the same silver paste as in Example 2 was prepared except that the amount of the phosphate ester dispersant was changed to 0.04% by mass.
When the viscosity of this bonding material (silver paste) was determined in the same manner as in Example 1, it was 230.6 (Pa · s) at 0.6 rpm (2.1 s −1 ) at 25 ° C. and 372.8 at 1 rpm. (Pa · s) 255.3 (Pa · s) at 2 rpm, 114.2 (Pa · s) at 5 rpm, 57.31 (Pa · s) at 6.4 rpm (20.1 s −1 ), 25 ° C. The ratio of the viscosity of 1 rpm to the viscosity of 5 rpm measured at 5 (Ti1) is 3.3, and the ratio of the viscosity of 2s −1 to the viscosity of 20 s −1 measured at 25 ° C. (Ti2) is 4.0. The printability (printability) of (silver paste) was good.
Using this bonding material (silver paste), a bonded body was obtained in the same manner as in Example 1. About this joined body, the void ratio of the joint surface was calculated by the same method as in Example 1 and the shear strength was measured. As a result, there was almost no void, the void ratio was very good at 0%, and the shear strength was It was as high as 34.1 MPa and good.
Comparative Example 4
A bonding material made of the same silver paste as in Example 2 was prepared except that the amount of the phosphate ester dispersant was 1% by mass and the acid dispersant was not added.
When the viscosity of this bonding material (silver paste) was determined by the same method as in Example 1, it was 15.58 (Pa · s) at 25 rpm and 0.6 rpm (2.1 s −1 ), and 10.85 at 1 rpm. (Pa · s) 6.408 (Pa · s) at 2 rpm, 3.405 (Pa · s) at 5 rpm, 2.907 (Pa · s) at 6.4 rpm (20.1 s −1 ), 25 ° C. The ratio (Ti1) of the viscosity of 1 rpm to the viscosity of 5 rpm measured in step 3.2 is 3.2, and the ratio of the viscosity of 2s −1 (Ti2) to the viscosity of 20 s −1 measured at 25 ° C. is 5.4. The printability (printability) of (silver paste) was good.
Using this bonding material (silver paste), a bonded body was obtained in the same manner as in Example 1. For this joined body, the void ratio of the joint surface was calculated by the same method as in Example 1 and the shear strength was measured. The void ratio was as high as 25.8%, which was not good, but the shear strength was 26. It was as high as 3 MPa and was good.
　アルコール溶剤として１−デカノールの代わりに１−オクタノール５．３５３質量％を使用した以外は、実施例２と同様の銀ペーストからなる接合材を用意した。
　この接合材（銀ペースト）の粘度を実施例１と同様の方法により求めたところ、２５℃において０．６ｒｐｍ（２．１ｓ−１）で３０３．７（Ｐａ・ｓ）、１ｒｐｍで２７３．２（Ｐａ・ｓ）、２ｒｐｍで１５６（Ｐａ・ｓ）、５ｒｐｍで６７．３４（Ｐａ・ｓ）、６．４ｒｐｍ（２０．１ｓ−１）で４９．２１（Ｐａ・ｓ）、２５℃で測定した５ｒｐｍの粘度に対する１ｒｐｍの粘度の比（Ｔｉ１）は４．１、２５℃で測定した２０ｓ−１の粘度に対する２ｓ−１の粘度の比（Ｔｉ２）は６．２であり、接合材（銀ペースト）の印刷性（印刷適性）は良好であった。
　この接合材（銀ペースト）を使用して、実施例１と同様の方法により接合体を得た。この接合体について、実施例１と同様の方法により、接合面のボイド率を算出し、シア強度を測定したところ、ボイドが殆どなく、ボイド率は０％と非常に良好であり、シア強度は２８．４ＭＰａと高く、良好であった。 A bonding material made of the same silver paste as in Example 2 was prepared except that 5.353 mass% of 1-octanol was used instead of 1-decanol as the alcohol solvent.
When the viscosity of the bonding material (silver paste) was determined in the same manner as in Example 1, it was 303.7 at 25 rpm and 0.6 rpm (2.1 s −1 ) at 30 rpm (27 · 1). (Pa · s) 156 (Pa · s) at 2 rpm, 67.34 (Pa · s) at 5 rpm, 49.21 (Pa · s) at 6.4 rpm (20.1 s −1 ), measured at 25 ° C. The ratio of the viscosity of 1 rpm to the viscosity of 5 rpm (Ti1) was 4.1, the ratio of the viscosity of 2s- 1 to the viscosity of 20s- 1 measured at 25 ° C. (Ti2) was 6.2, and the bonding material (silver The printability (printability) of the paste) was good.
Using this bonding material (silver paste), a bonded body was obtained in the same manner as in Example 1. About this joined body, the void ratio of the joint surface was calculated by the same method as in Example 1 and the shear strength was measured. As a result, there was almost no void, the void ratio was very good at 0%, and the shear strength was It was as high as 28.4 MPa.
　アルコール溶剤としての１−デカノール５．３５３質量％の代わりに、１−デカノール２．６７６５質量％とテルペン系のアルコール（日本テルペン化学株式会社製のＴＯＥ−１００（ガムテルピン油とエチレングリコールから誘導されたテルペンエーテル））２．６７６５質量％を使用した以外は、実施例２と同様の銀ペーストからなる接合材を用意した。
　この接合材（銀ペースト）の粘度を実施例１と同様の方法により求めたところ、２５℃において０．６ｒｐｍ（２．１ｓ−１）で３７７（Ｐａ・ｓ）、１ｒｐｍで２６６．９（Ｐａ・ｓ）、２ｒｐｍで１４６（Ｐａ・ｓ）、５ｒｐｍで６３．１９（Ｐａ・ｓ）、６．４ｒｐｍ（２０．１ｓ−１）で５０．５５（Ｐａ・ｓ）、２５℃で測定した５ｒｐｍの粘度に対する１ｒｐｍの粘度の比（Ｔｉ１）は４．２、２５℃で測定した２０ｓ−１の粘度に対する２ｓ−１の粘度の比（Ｔｉ２）は７．５であり、接合材（銀ペースト）の印刷性（印刷適性）は良好であった。
　この接合材（銀ペースト）を使用して、実施例１と同様の方法により接合体を得た。この接合体について、実施例１と同様の方法により、接合面のボイド率を算出し、シア強度を測定したところ、ボイドが殆どなく、ボイド率は０％と非常に良好であり、シア強度は４９．７ＭＰａと高く、良好であった。 Instead of 5.353% by mass of 1-decanol as an alcohol solvent, 2.6765% by mass of 1-decanol and terpene alcohol (TOE-100 manufactured by Nippon Terpene Chemical Co., Ltd. (derived from gum terpin oil and ethylene glycol) A joining material made of the same silver paste as in Example 2 was prepared except that terpene ether)) 2.6765% by mass was used.
When the viscosity of this bonding material (silver paste) was determined in the same manner as in Example 1, it was 377 (Pa · s) at 0.6 rpm (2.1 s −1 ) at 25 ° C. and 266.9 (Pa · s) at 1 rpm. S) 146 (Pa · s) at 2 rpm, 63.19 (Pa · s) at 5 rpm, 50.55 (Pa · s) at 6.4 rpm (20.1 s −1 ), 5 rpm measured at 25 ° C. The ratio of the viscosity at 1 rpm to the viscosity (Ti1) is 4.2, the ratio of the viscosity of 2s- 1 to the viscosity of 20s- 1 measured at 25 ° C (Ti2) is 7.5, and the bonding material (silver paste) The printability (printability) of was good.
Using this bonding material (silver paste), a bonded body was obtained in the same manner as in Example 1. About this joined body, the void ratio of the joint surface was calculated by the same method as in Example 1 and the shear strength was measured. As a result, there was almost no void, the void ratio was very good at 0%, and the shear strength was It was as high as 49.7 MPa and was good.
　ヘキサン酸で被覆された銀微粒子の量を２０．１０８質量％、オレイン酸で被覆された銀粒子の量を７３．３９２質量％、焼成助剤（添加剤）としてのジグリコール酸（ＤＧＡ）（ジカルボン酸）の量を０．０６２質量％、酸系分散剤の量を０．９２９質量％、リン酸エステル系分散剤の量を０．０７４質量％、溶剤としてトリオールの量を０．４６４質量％とし、アルコール溶剤としての１−デカノール５．３５３質量％の代わりに、１−デカノール２．４８５質量％とテルペン系のアルコール（日本テルペン化学株式会社製のＴＯＥ−１００）２．４８５質量％を使用した以外は、実施例２と同様の銀ペーストからなる接合材を用意した。
　この接合材（銀ペースト）の粘度を実施例１と同様の方法により求めたところ、２５℃において０．６ｒｐｍ（２．１ｓ−１）で６０２．４（Ｐａ・ｓ）、１ｒｐｍで４９７．１（Ｐａ・ｓ）、２ｒｐｍで２３２．６（Ｐａ・ｓ）、５ｒｐｍで７９．２６（Ｐａ・ｓ）、６．４ｒｐｍ（２０．１ｓ−１）で５６．７８（Ｐａ・ｓ）、２５℃で測定した５ｒｐｍの粘度に対する１ｒｐｍの粘度の比（Ｔｉ１）は６．３、２５℃で測定した２０ｓ−１の粘度に対する２ｓ−１の粘度の比（Ｔｉ２）は１０．６であり、接合材（銀ペースト）の印刷性（印刷適性）は良好であった。
　この接合材（銀ペースト）を使用して、実施例１と同様の方法により接合体を得た。この接合体について、実施例１と同様の方法により、接合面のボイド率を算出し、シア強度を測定したところ、ボイドが殆どなく、ボイド率は０％と非常に良好であり、シア強度は７８．１ＭＰａと高く、良好であった。 The amount of silver fine particles coated with hexanoic acid is 20.108% by mass, the amount of silver particles coated with oleic acid is 73.392% by mass, and diglycolic acid (DGA) as a baking aid (additive) ( The amount of dicarboxylic acid) is 0.062% by mass, the amount of acid dispersant is 0.929% by mass, the amount of phosphate ester dispersant is 0.074% by mass, and the amount of triol as a solvent is 0.464% by mass. In place of 5.353% by mass of 1-decanol as an alcohol solvent, 2.485% by mass of 1-decanol and 2.485% by mass of terpene alcohol (TOE-100 manufactured by Nippon Terpene Chemical Co., Ltd.) A bonding material made of the same silver paste as in Example 2 was prepared except that it was used.
When the viscosity of this bonding material (silver paste) was determined in the same manner as in Example 1, it was 602.4 (Pa · s) at 0.6 rpm (2.1 s −1 ) at 25 ° C. and 497.1 at 1 rpm. (Pa · s) 232.6 (Pa · s) at 2 rpm, 79.26 (Pa · s) at 5 rpm, 56.78 (Pa · s) at 6.4 rpm (20.1 s −1 ), 25 ° C. The ratio (Ti1) of the viscosity at 1 rpm to the viscosity at 5 rpm measured at 6.3 was 6.3, and the ratio (Ti2) of 2s −1 to the viscosity of 20 s −1 measured at 25 ° C. was 10.6. The printability (printability) of (silver paste) was good.
Using this bonding material (silver paste), a bonded body was obtained in the same manner as in Example 1. About this joined body, the void ratio of the joint surface was calculated by the same method as in Example 1 and the shear strength was measured. As a result, there was almost no void, the void ratio was very good at 0%, and the shear strength was It was as high as 78.1 MPa.
　ヘキサン酸で被覆された銀微粒子の量を２０．２１５質量％、オレイン酸で被覆された銀粒子の量を７３．７８５質量％、焼成助剤（添加剤）としてのジグリコール酸（ＤＧＡ）（ジカルボン酸）の量を０．０５７質量％、酸系分散剤の量を０．８５７質量％、リン酸エステル系分散剤の量を０．０６９質量％、溶剤としてトリオールの量を０．４２９質量％とし、アルコール溶剤としての１−デカノール５．３５３質量％の代わりに、１−デカノール２．２９５質量％とテルペン系のアルコール（日本テルペン化学株式会社製のＴＯＥ−１００）２．２９５質量％を使用した以外は、実施例２と同様の銀ペーストからなる接合材を用意した。
　この接合材（銀ペースト）の粘度を実施例１と同様の方法により求めたところ、２５℃において０．６ｒｐｍ（２．１ｓ−１）で７９４（Ｐａ・ｓ）、１ｒｐｍで６５１．７（Ｐａ・ｓ）、２ｒｐｍで３５０．７（Ｐａ・ｓ）、５ｒｐｍで９８．１１（Ｐａ・ｓ）、６．４ｒｐｍ（２０．１ｓ−１）で５０．１２（Ｐａ・ｓ）、２５℃で測定した５ｒｐｍの粘度に対する１ｒｐｍの粘度の比（Ｔｉ１）は６．６、２５℃で測定した２０ｓ−１の粘度に対する２ｓ−１の粘度の比（Ｔｉ２）は１５．８であり、接合材（銀ペースト）の印刷性（印刷適性）は良好であった。
　この接合材（銀ペースト）を使用して、実施例１と同様の方法により接合体を得た。この接合体について、実施例１と同様の方法により、接合面のボイド率を算出し、シア強度を測定したところ、ボイドが殆どなく、ボイド率は０％と非常に良好であり、シア強度は２６．６ＭＰａと高く、良好であった。
　これらの実施例および比較例の接合材の製造条件および特性を表１~表４に示す。なお、表４において、接合材の粘度、印刷性および接合面のボイド率が良好な場合を「○」、良好でない場合を「×」で示している。
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
 The amount of silver fine particles coated with hexanoic acid was 20.215% by mass, the amount of silver particles coated with oleic acid was 73.785% by mass, and diglycolic acid (DGA) as a baking aid (additive) ( The amount of dicarboxylic acid) is 0.057% by mass, the amount of acid dispersant is 0.857% by mass, the amount of phosphate ester dispersant is 0.069% by mass, and the amount of triol as a solvent is 0.429% by mass. In place of 5.353% by mass of 1-decanol as an alcohol solvent, 2.295% by mass of 1-decanol and 2.295% by mass of terpene alcohol (TOE-100 manufactured by Nippon Terpene Chemical Co., Ltd.) A bonding material made of the same silver paste as in Example 2 was prepared except that it was used.
When the viscosity of this bonding material (silver paste) was determined in the same manner as in Example 1, 794 (Pa · s) at 0.6 rpm (2.1 s −1 ) at 25 ° C. and 651.7 (Pa) at 1 rpm. S) 350.7 (Pa · s) at 2 rpm, 98.11 (Pa · s) at 5 rpm, 50.12 (Pa · s) at 6.4 rpm (20.1 s −1 ), measured at 25 ° C. The ratio of the viscosity of 1 rpm to the viscosity of 5 rpm (Ti1) was 6.6, the ratio of the viscosity of 2s −1 to the viscosity of 20 s −1 measured at 25 ° C. (Ti2) was 15.8, and the bonding material (silver The printability (printability) of the paste) was good.
Using this bonding material (silver paste), a bonded body was obtained in the same manner as in Example 1. About this joined body, the void ratio of the joint surface was calculated by the same method as in Example 1 and the shear strength was measured. As a result, there was almost no void, the void ratio was very good at 0%, and the shear strength was It was as high as 26.6 MPa and was good.
Tables 1 to 4 show the manufacturing conditions and characteristics of the bonding materials of these examples and comparative examples. In Table 4, the case where the viscosity of the bonding material, the printability, and the void ratio of the bonding surface are good is indicated by “◯”, and the case where it is not good is indicated by “X”.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004

Claims (15)

  1. 平均一次粒子径１~５０ｎｍの銀微粒子と平均一次粒子径０．５~４μｍの銀粒子と溶剤と分散剤を含む銀ペーストからなる接合材において、銀微粒子の含有量が５~３０質量％、銀粒子の含有量が６０~９０質量％、銀微粒子と銀粒子の合計の含有量が９０質量％以上であることを特徴とする、接合材。 In a bonding material comprising silver fine particles having an average primary particle diameter of 1 to 50 nm, silver particles having an average primary particle diameter of 0.5 to 4 μm, a solvent and a dispersant, the content of silver fine particles is 5 to 30% by mass, A bonding material, wherein the content of silver particles is 60 to 90% by mass, and the total content of silver fine particles and silver particles is 90% by mass or more.
  2. 前記分散剤が酸系分散剤とリン酸エステル系分散剤とからなることを特徴とする、請求項１に記載の接合材。 The bonding material according to claim 1, wherein the dispersant comprises an acid-based dispersant and a phosphate ester-based dispersant.
  3. 前記リン酸エステル系分散剤の量が前記銀ペーストに対して０．０１~０．１質量％であることを特徴とする、請求項２に記載の接合材。 The bonding material according to claim 2, wherein the amount of the phosphoric acid ester dispersant is 0.01 to 0.1% by mass with respect to the silver paste.
  4. 前記酸系分散剤の量が前記銀ペーストに対して０．５~２質量％であることを特徴とする、請求項２に記載の接合材。 The bonding material according to claim 2, wherein the amount of the acid-based dispersant is 0.5 to 2% by mass with respect to the silver paste.
  5. 前記銀ペーストが焼結助剤を含むことを特徴とする、請求項１に記載の接合材。 The bonding material according to claim 1, wherein the silver paste contains a sintering aid.
  6. 前記焼結助剤がジグリコール酸であることを特徴とする、請求項５に記載の接合材。 The joining material according to claim 5, wherein the sintering aid is diglycolic acid.
  7. 前記焼結助剤の量が前記銀ペーストに対して０．０１~０．１質量％であることを特徴とする、請求項５に記載の接合材。 6. The bonding material according to claim 5, wherein the amount of the sintering aid is 0.01 to 0.1% by mass with respect to the silver paste.
  8. 前記溶剤がアルコールとトリオールとからなることを特徴とする、請求項１に記載の接合材。 The bonding material according to claim 1, wherein the solvent is made of alcohol and triol.
  9. 前記銀微粒子が炭素数８以下の有機化合物で被覆されていることを特徴とする、請求項１に記載の接合材。 The bonding material according to claim 1, wherein the silver fine particles are coated with an organic compound having 8 or less carbon atoms.
  10. 前記銀微粒子を被覆する有機化合物がヘキサン酸であることを特徴とする、請求項９に記載の接合材。 The bonding material according to claim 9, wherein the organic compound covering the silver fine particles is hexanoic acid.
  11. 前記銀粒子が有機化合物で被覆されていることを特徴とする、請求項１に記載の接合材。 The bonding material according to claim 1, wherein the silver particles are coated with an organic compound.
  12. 前記銀粒子を被覆する有機化合物がオレイン酸であることを特徴とする、請求項１１に記載の接合材。 The bonding material according to claim 11, wherein the organic compound covering the silver particles is oleic acid.
  13. 前記接合材を被接合物間に介在させて加熱することにより、前記接合材中の銀を焼結させて銀接合層を介して被接合物同士を接合したときに、銀接合層の接合面の面積に対してボイドが占める面積の割合が１０％未満であることを特徴とする、請求項１に記載の接合材。 When the bonding material is interposed between the objects to be bonded and heated, the silver in the bonding material is sintered and the objects to be bonded are bonded to each other via the silver bonding layer. 2. The bonding material according to claim 1, wherein a ratio of an area occupied by the void to an area of less than 10%.
  14. 前記接合材の粘度をレオメーターにより２５℃において６．４ｒｐｍで測定したときの粘度が１００Ｐａ・ｓ以下であることを特徴とする、請求項１に記載の接合材。 2. The bonding material according to claim 1, wherein the viscosity of the bonding material is 100 Pa · s or less when measured at 6.4 rpm at 25 ° C. with a rheometer.
  15. 請求項１乃至１４のいずれかに記載の接合材を被接合物間に介在させて加熱することにより、接合材中の銀を焼結させて銀接合層を形成し、この銀接合層により被接合物同士を接合することを特徴とする、接合方法。 The bonding material according to claim 1 is interposed between the objects to be bonded and heated to sinter the silver in the bonding material to form a silver bonding layer. A joining method, comprising joining joined objects.
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